A method for continuous production of sulfuryl fluoride by a dynamic tubular reactor

Abstract

The application provides a method for continuously preparing sulfuryl fluoride in a dynamic tubular reactor, comprising the following steps: preheating the dynamic tubular reactor to 140-280 DEG C, then inputting 20-200 mesh hydrogen fluoride salt and sulfonyl chloride into the dynamic tubular reactor for reaction, after the reaction is completed, carrying out gas-solid separation, washing and drying the obtained gas, and obtaining sulfuryl fluoride; wherein the molar ratio of hydrogen fluoride salt to sulfonyl chloride is 2-4:1; the hydrogen fluoride salt is selected from inorganic hydrogen fluoride salt or amine hydrogen fluoride salt; and the material residence time is 5-60 s. The method for preparing sulfuryl fluoride adopts inorganic hydrogen fluoride salt in combination with preheating temperature, material molar ratio and particle size limitation of hydrogen fluoride salt; so that the whole reaction process does not need organic solvent and toxic gas raw material, the process has high reliability and safety, has low requirement on equipment, and the by-product fluorinated salt obtained in the reaction can be recycled and used as resources.

Description

Technical Field

[0001] This invention relates to the field of chemical engineering, and more particularly to a method for the continuous preparation of thioyl fluoride using a dynamic tubular reactor. Background Technology

[0002] Sulfonyl fluoride is an inorganic compound with the chemical formula SO₂F₂. It is a colorless and odorless gas at room temperature and pressure, possessing broad-spectrum insecticidal properties, strong diffusion, low toxicity, minimal residue, a wide operating temperature range, and is non-flammable, non-explosive, and non-corrosive. It is increasingly widely used in warehouses, cargo ships, containers, buildings, reservoir dams, termite control, and the control of overwintering pests and trunk-boring pests in gardens and trees. Furthermore, sulfuryl fluoride can also be used as a raw material in the manufacture of lithium-ion battery additives, showing broad application prospects in the field of new energy materials.

[0003] Currently, common methods for preparing sulfuryl fluoride include: the direct fluorination method using sulfur dioxide and fluorine as main raw materials; the anhydrous hydrofluoric acid method using sulfur dioxide, chlorine, and anhydrous hydrofluoric acid as raw materials; the nitrosyl fluoride method using sulfur dioxide and nitrosyl fluoride as main raw materials; and the fluorosulfonic acid method using fluorosulfonic acid and barium chloride as main raw materials. However, existing processes for preparing sulfuryl fluoride require the use of organic solvents, which are not environmentally friendly, or require the use of highly toxic substances such as chlorine, sulfur dioxide, and gaseous hydrogen fluoride, which places high demands on equipment and is not suitable for industrial production. Summary of the Invention

[0004] The purpose of this invention is to provide a method for the continuous preparation of thioyl fluoride using a dynamic tubular reactor. This method is relatively safe, does not require organic solvents or highly toxic gases, has low equipment requirements, and is conducive to industrial production.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A method for continuous preparation of thioyl fluoride using a dynamic tubular reactor includes the following steps:

[0007] The dynamic tubular reactor is preheated to 140-280℃, and then hydrogen fluoride salt and sulfonyl chloride are simultaneously introduced into the dynamic tubular reactor for reaction. After the reaction is completed, gas-solid separation is performed, and the obtained gas is washed and dried with alkaline solution to obtain sulfonyl fluoride.

[0008] The molar ratio of the hydrogen fluoride salt to the sulfonyl chloride is 2-4:1, and the mesh size of the hydrogen fluoride salt is 20-200. The hydrogen fluoride salt is selected from inorganic hydrogen fluoride salts or amine hydrogen fluoride salts. The residence time of the mixture of the hydrogen fluoride salt and the sulfonyl chloride in the dynamic tubular reactor is 5-60 s.

[0009] The main reaction equation for the preparation of thioyl fluoride is as follows:

[0010] SO₂Cl₂ + 2XHF₂ → SO₂F₂ + 2HCl + 2XF

[0011] The main side reactions are:

[0012] SO₂Cl₂ + XHF₂ → SO₂FCl + HCl + XF

[0013] By controlling the preheating temperature of the dynamic tubular reactor, the molar ratio of hydrogen fluoride salt to sulfonyl chloride, the type and particle size of hydrogen fluoride salt, and the residence time of hydrogen fluoride salt and sulfonyl chloride in the tubular reactor (the specific residence time is controlled by controlling the rotation speed of the tubular reactor), it is possible to ensure that the materials are in full contact and react, and at the same time, the intermediate products will undergo the following reaction, thereby directing the reaction in a direction that is conducive to the formation of the target product, thioyl fluoride.

[0014] SO₂FCl + XHF₂ → SO₂F₂ + HCl + XF

[0015] Optionally, the inorganic salt of hydrogen fluoride includes, but is not limited to, sodium hydrogen fluoride and / or potassium hydrogen fluoride; potassium hydrogen fluoride is preferred.

[0016] Optionally, the reaction temperature is 140-280℃.

[0017] Optionally, the residence time of the mixture of the hydrogen fluoride salt and the sulfonyl chloride in the dynamic tubular reactor is 25-60 s.

[0018] Optionally, the hydrogen fluoride salt is fed into the dynamic tubular reactor via a solid feed pump.

[0019] Optionally, the sulfonyl chloride is fed into the dynamic tubular reactor via a liquid feed pump.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] The present invention provides a method for the continuous preparation of sulfonyl fluoride using a dynamic tubular reactor. By employing inorganic hydrogen fluoride salts or ammonium hydrogen fluoride, combined with the preheating temperature of the dynamic tubular reactor, and the molar ratio of hydrogen fluoride salt to sulfonyl chloride and the particle size limitation of hydrogen fluoride salt, the entire reaction process does not require organic solvents or highly toxic gases. The process has high reliability and safety, low equipment requirements (existing equipment is sufficient), greatly improved raw material safety and stability, and the by-product fluoride salts (such as KF, NaF, etc.) obtained from the reaction can be recovered and utilized for resource utilization, which helps to reduce production costs. The addition and discharge of materials are continuous, providing a basis for continuous production. Attached Figure Description

[0022] Figure 1 This is a gas chromatogram of the thioyl fluoride obtained in Example 1 of the present invention;

[0023] Figure 2 This is a gas chromatogram of the thioyl fluoride obtained in Example 2 of the present invention;

[0024] Figure 3 This is a gas chromatogram of the thioyl fluoride obtained in Example 3 of the present invention;

[0025] Figure 4 This is a gas chromatogram of the thioyl fluoride prepared in Comparative Example 1 of the present invention. Detailed Implementation

[0026] The present invention will now be described in detail through embodiments. It should be noted that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description.

[0027] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0028] Example 1

[0029] Weigh out 40.0 g (80 mesh) of potassium hydrogen fluoride and 27.0 g of sulfonyl chloride for later use. Preheat the dynamic tubular reactor to 260℃. Set the feed rate of the solid feeder (for adding solid potassium hydrogen fluoride to the reactor) connected to the reactor to 4.0 g / min and the feed rate of the liquid feeder (for adding liquid sulfonyl chloride to the reactor) to 2.8 g / min. Start the reactor, then start the liquid feeder first, followed by the solid feeder. Adjust the reactor speed to ensure that the raw materials remain in the reactor for 20 seconds at this temperature before being discharged. Separate the generated product into gas and solid phases using a cyclone separator. After washing the gas phase with alkaline solution, dry it through a packed column filled with calcium chloride to obtain sulfonyl fluoride. Gas chromatography analysis showed its purity to be 70.36%. Figure 1 The yield was 69%.

[0030] Example 2

[0031] Weigh out 590.0 g (200 mesh) of potassium hydrogen fluoride and 270.0 g of sulfonyl chloride for later use. Preheat the dynamic tubular reactor to 220℃. Set the feed rate of the solid feeder (for adding solid potassium hydrogen fluoride to the reactor) connected to the reactor to 20.0 g / min and the feed rate of the liquid feeder (for adding liquid sulfonyl chloride to the reactor) to 9.1 g / min. Start the reactor, then start the liquid feeder first, followed by the solid feeder. Adjust the reactor speed to ensure that the raw materials remain in the reactor for 40 seconds at this temperature before being discharged. Separate the generated product into gas and solid phases using a cyclone separator. After washing the gas phase with alkaline solution, dry it through a packed column filled with calcium chloride to obtain sulfonyl fluoride. Gas chromatography analysis showed its purity to be 89.54%. Figure 2 The yield was 76%.

[0032] Example 3

[0033] Weigh out 860.0 g (20 mesh) of potassium hydrogen fluoride and 680.0 g of sulfonyl chloride for later use. Preheat the dynamic tubular reactor to 200℃. Set the feed rate of the solid feeder (for adding solid potassium hydrogen fluoride to the reactor) connected to the reactor to 29.0 g / min and the feed rate of the liquid feeder (for adding liquid sulfonyl chloride to the reactor) to 22.8 g / min. Start the reactor, then start the liquid feeder first, followed by the solid feeder. Adjust the reactor speed to ensure that the raw materials remain in the reactor for 15 seconds at this temperature before being discharged. Separate the generated product into gas and solid phases using a cyclone separator. After washing the gas phase with alkaline solution, dry it through a packed column filled with calcium chloride to obtain sulfonyl fluoride. Gas chromatography analysis showed its purity to be 73.62%. Figure 3 The yield was 66%.

[0034] Example 4

[0035] Weigh out 250.0 g (150 mesh) of potassium hydrogen fluoride and 140.0 g of sulfonyl chloride for later use. Preheat the dynamic tubular reactor to 210℃. Set the feed rate of the solid feeder (for adding solid sodium hydrogen fluoride to the reactor) connected to the reactor to 25.0 g / min and the feed rate of the liquid feeder (for adding liquid sulfonyl chloride to the reactor) to 14.0 g / min. Start the reactor, then start the liquid feeder first, followed by the solid feeder. Adjust the reactor speed to ensure that the raw materials remain in the reactor for 60 seconds at this temperature before being discharged. Separate the generated product into gas and solid phases using a cyclone separator. After washing the gas phase with alkaline solution, dry it through a packed column filled with calcium chloride to obtain sulfonyl fluoride. Gas chromatography analysis showed that its purity was 86% and the yield was 76%.

[0036] Example 5

[0037] Weigh out 468.0 g (100 mesh) of potassium hydrogen fluoride and 340.0 g of sulfonyl chloride for later use. Preheat the dynamic tubular reactor to 240℃. Set the feed rate of the solid feeder (for adding solid sodium hydrogen fluoride to the reactor) connected to the reactor to 23.5 g / min and the feed rate of the liquid feeder (for adding liquid sulfonyl chloride to the reactor) to 17.0 g / min. Start the reactor, then start the liquid feeder first, followed by the solid feeder. Adjust the reactor speed to ensure that the raw materials remain in the reactor for 30 seconds at this temperature before being discharged. Separate the generated product into gas and solid phases using a cyclone separator. After washing the gas phase with alkaline solution, dry it through a packed column filled with calcium chloride to obtain sulfonyl fluoride. Gas chromatography analysis showed that its purity was 81% and the yield was 74%.

[0038] Example 6

[0039] Weigh out 220.0 g (100 mesh) of sodium bifluoride and 198.0 g of sulfonyl chloride for later use. Preheat the dynamic tubular reactor to 240°C. Set the feed rate of the solid feeder (for adding solid sodium bifluoride to the reactor) connected to the reactor to 11.0 g / min and the feed rate of the liquid feeder (for adding liquid sulfonyl chloride to the reactor) to 9.9 g / min. Start the reactor, then start the liquid feeder first, followed by the solid feeder. Adjust the reactor speed to ensure that the raw materials remain in the reactor for 30 seconds at this temperature before being discharged. Separate the generated product into gas and solid phases using a cyclone separator. After washing the gas phase with alkaline solution, dry it through a packed column filled with calcium chloride to obtain sulfonyl fluoride. Gas chromatography analysis showed that its purity was 76% and the yield was 88%.

[0040] Example 7

[0041] Weigh out 513.0 g (80 mesh) of ammonium bifluoride and 405.0 g of sulfonyl chloride for later use. Preheat the dynamic tubular reactor to 200°C. Set the feed rate of the solid feeder (for adding solid sodium bifluoride to the reactor) connected to the reactor to 17.0 g / min and the feed rate of the liquid feeder (for adding liquid sulfonyl chloride to the reactor) to 13.6 g / min. Start the reactor, then start the liquid feeder first, followed by the solid feeder. Adjust the reactor speed to ensure that the raw materials remain in the reactor for 30 seconds at this temperature before being discharged. Separate the generated product into gas and solid phases using a cyclone separator. After washing the gas phase with alkaline solution, dry it through a packed column filled with calcium chloride to obtain sulfonyl fluoride. Gas chromatography analysis showed that its purity was 72% and the yield was 74%.

[0042] Example 8

[0043] Weigh out 440.0 g (45 mesh) of potassium hydrogen fluoride and 270.0 g of sulfonyl chloride for later use. Preheat the dynamic tubular reactor to 220℃. Set the feed rate of the solid feeder (for adding solid sodium hydrogen fluoride to the reactor) connected to the reactor to 22.0 g / min and the feed rate of the liquid feeder (for adding liquid sulfonyl chloride to the reactor) to 13.5 g / min. Start the reactor, then start the liquid feeder first, followed by the solid feeder. Adjust the reactor speed to ensure that the raw materials remain in the reactor for 8 seconds at this temperature before being discharged. Separate the generated product into gas and solid phases using a cyclone separator. After washing the gas phase with alkaline solution, dry it through a packed column filled with calcium chloride to obtain sulfonyl fluoride. Gas chromatography analysis showed that its purity was 82% and the yield was 43%.

[0044] Example 9

[0045] Weigh out 220.0 g (45 mesh) of potassium hydrogen fluoride and 135.0 g of sulfonyl chloride for later use. Preheat the dynamic tubular reactor to 280℃. Set the feed rate of the solid feeder (for adding solid sodium hydrogen fluoride to the reactor) connected to the reactor to 8.6 g / min and the feed rate of the liquid feeder (for adding liquid sulfonyl chloride to the reactor) to 5.4 g / min. Start the reactor, then start the liquid feeder first, followed by the solid feeder. Adjust the reactor speed to ensure that the raw materials remain in the reactor for 40 seconds at this temperature before being discharged. Separate the generated product into gas and solid phases using a cyclone separator. After washing the gas phase with alkaline solution, dry it through a packed column filled with calcium chloride to obtain sulfonyl fluoride. Gas chromatography analysis showed that its purity was 83% and the yield was 64%.

[0046] Example 10

[0047] Weigh out 685.0 g (20 mesh) of ammonium bifluoride and 405 g of sulfonyl chloride for later use. Preheat the dynamic tubular reactor to 140°C. Set the feed rate of the solid feeder (for adding solid sodium bifluoride to the reactor) connected to the reactor to 17.0 g / min and the feed rate of the liquid feeder (for adding liquid sulfonyl chloride to the reactor) to 10.2 g / min. Start the reactor, then start the liquid feeder first, followed by the solid feeder. Adjust the reactor speed to ensure that the raw materials remain in the reactor for 30 seconds at this temperature before being discharged. Separate the generated product into gas and solid phases using a cyclone separator. After washing the gas phase with alkaline solution, dry it through a packed column filled with calcium chloride to obtain sulfonyl fluoride. Gas chromatography analysis showed that its purity was 76% and the yield was 80%.

[0048] Example 11

[0049] Weigh out 8.9 kg (200 mesh) of potassium hydrogen fluoride and 4.0 kg of sulfonyl chloride for later use. Preheat the dynamic tubular reactor to 220°C. Set the feed rate of the solid feeder (for adding solid potassium hydrogen fluoride to the reactor) connected to the reactor to 100.0 g / min and the feed rate of the liquid feeder (for adding liquid sulfonyl chloride to the reactor) to 45.0 g / min. Start the reactor, then start the liquid feeder first, followed by the solid feeder. Adjust the reactor speed to ensure that the raw materials remain in the reactor for 40 seconds at this temperature before being discharged. Separate the generated product into gas and solid phases using a cyclone separator. After washing the gas phase with alkaline solution, dry it through a packed column filled with calcium chloride to obtain sulfonyl fluoride. Gas chromatography analysis showed that its purity was 92% and the yield was 78%.

[0050] Comparative Example 1

[0051] This comparative example is similar to Example 2, except that the preheating temperature of the dynamic tubular reactor is different. In this comparative example, the dynamic tubular reactor is preheated to 125°C, and the final purity of the obtained thiocyanate fluoride is 15.68%. Figure 4 The yield was 38%.

[0052] Comparative Example 2

[0053] This comparative example is similar to Example 2, except that the preheating temperature of the dynamic tubular reactor is different. In this comparative example, the dynamic tubular reactor is preheated to 300°C, and the final sulfuryl fluoride has a purity of 56% and a yield of 60%.

[0054] Comparative Example 3

[0055] This comparative example is similar to Example 2, except that the potassium hydrogen fluoride has a different particle size. In this comparative example, the potassium hydrogen fluoride is 10 mesh, and the final sulfuryl fluoride has a purity of 35% and a yield of 48%.

[0056] Comparative Example 4

[0057] This comparative example is similar to Example 2, except that the potassium hydrogen fluoride particle size is different. In this comparative example, the potassium hydrogen fluoride is 300 mesh, and the final sulfuryl fluoride has a purity of 55% and a yield of 68%. Solid discharge is relatively difficult.

[0058] Comparative Example 5

[0059] This comparative example is similar to Example 2, except that the residence time of the material in the dynamic tubular reactor is different. In this comparative example, the residence time is 3s, and the final sulfuryl fluoride has a purity of 25% and a yield of 22%.

[0060] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A method for continuous preparation of thioyl fluoride using a dynamic tubular reactor, characterized in that, Includes the following steps: The dynamic tubular reactor is preheated to 200-280℃, and then hydrogen fluoride salt and sulfonyl chloride are fed into the dynamic tubular reactor for reaction. After the reaction is completed, gas-solid separation is performed, and the obtained gas is washed and dried to obtain sulfonyl fluoride. The molar ratio of the hydrogen fluoride salt to the sulfonyl chloride is 2-4:1, and the mesh size of the hydrogen fluoride salt is 20-200; the hydrogen fluoride salt is selected from inorganic hydrogen fluoride salts. The residence time of the mixture of the hydrogen fluoride salt and the sulfonyl chloride in the dynamic tubular reactor is 15-60 s; The inorganic salt of hydrogen fluoride is selected from sodium hydrogen fluoride and / or potassium hydrogen fluoride.

2. The method for continuous preparation of thioyl fluoride using a dynamic tubular reactor as described in claim 1, characterized in that, The inorganic salt of hydrogen fluoride is potassium hydrogen fluoride.

3. The method for continuous preparation of thioyl fluoride using a dynamic tubular reactor as described in claim 1, characterized in that, The residence time of the mixture of the hydrogen fluoride salt and the sulfonyl chloride in the dynamic tubular reactor is 25-60 s.

4. The method for continuous preparation of thioyl fluoride using a dynamic tubular reactor as described in claim 1, characterized in that, The hydrogen fluoride salt is fed into the dynamic tubular reactor via a solid feed pump.

5. The method for continuous preparation of thioyl fluoride using a dynamic tubular reactor as described in claim 1, characterized in that, The sulfonyl chloride is fed into the dynamic tubular reactor via a liquid feed pump.

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